Because of the low temperature operation, proton exchange membrane (PEM) fuel cell has a water phase transition. Therefore, water management is an important operation issue in a PEM fuel cell because the liquid water in the fuel cell causes electrode flooding that can lower the cell performance under high current density conditions. In this study, in order to understand the reactant distributions in the cathode channels of the PEM fuel cell, an experimental technique that can measure the species concentrations of reactant gases by using gas chromatograph (GC) is applied for an operating PEM fuel cell. The oxygen distribution along the cathode flow channels of PEM fuel cell is mainly investigated with various operating conditions. Also, the relations between cathode flooding and oxygen concentrations and oxygen consumption pattern along the cathode channel configurations of the unit cell adopted for this study are discussed using GC measurement and visualization experiment of cathode flooding. It is found that the amount of oxygen consumption is very sensitive to various operating conditions of the fuel cell and was much affected by the flooding occurrence in cathode channels.